CN104073770A - Tiwaln hard thin film and preparation method thereof - Google Patents
Tiwaln hard thin film and preparation method thereof Download PDFInfo
- Publication number
- CN104073770A CN104073770A CN201410282805.XA CN201410282805A CN104073770A CN 104073770 A CN104073770 A CN 104073770A CN 201410282805 A CN201410282805 A CN 201410282805A CN 104073770 A CN104073770 A CN 104073770A
- Authority
- CN
- China
- Prior art keywords
- target
- sputtering power
- tiwaln
- thin film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention discloses a TiWAlN hard thin film and a preparation method thereof. The preparation method comprises the following steps: by taking high-purity Ti target, W target and Al target as targets, depositing on a hard alloy or a ceramic matrix by adopting a double-target confocal radio frequency reaction sputtering method, wherein the molecular formula of the film is Ti(W, Al, N), and the thickness of the film is 1-3mu m; deposition is performed by arcing through argon and by taking nitrogen as reactive gas when the vacuum degree is superior to 3.0*10<-5>Pa during deposition, the sputtering pressure is 0.3Pa, the argon-nitrogen flow ratio is 10:(1-3), the sputtering power of the Ti target is 230-280W, the sputtering power of the W target is 80-100W, and the sputtering power of the Al target is 0-100W. The obtained hard coating comprehensively has excellent characteristics of high hardness and high wear resistance.
Description
Technical field
The present invention relates to a kind of coating and preparation method thereof, particularly a kind of TiWAlN hard nanometer structure composite film and preparation method, belong to ceramic coating technical field.
Background technology
Development along with modern processing, the appearance of high-performance machining mode under the extreme service condition of high temperature particularly at a high speed,, require the coating of tool surface should there is higher hardness, good friction and wear behavior, and have good high temperature oxidation resistance concurrently.Yet, although existing cutter coat has higher hardness, but their friction and wear behavior is all undesirable, because causing film, high temperature oxidation comes off from tool surface simultaneously, greatly reduce the use properties of cutter, sharply shorten its work-ing life, cannot meet the requirement that modern machining is higher.In recent years a lot of scholar's research the impact of Al element on film performance, discovery is added Al element in film, not only improved the antioxidant property of film, mechanical property and the friction and wear behavior of film all improve simultaneously, yet, the oxide compound Al forming in film antioxidation process for Al element
2o
3structure by amorphous to the transformation of crystalline state with and friction and wear behavior affected to aspect seldom have discussion.At present, on market, also do not find that TiWAlN film is used as cutting tool coating material.Therefore, compare with the desired desirable high-hardness wear-resistant coating of contemporary processing manufacturing industry, this kind of hard coat has good researching value.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of TiWAlN hard nanometer structural membrane and preparation method are provided, overcome existing TiN and be the shortcoming such as hard nanometer structure composite film and multilayer film friction and wear behavior be undesirable, have compared with high efficiency, have high rigidity and excellent friction and wear behavior concurrently, can be used as the nanostructure ganoine thin film of high speed, DRY CUTTING.
The present invention is achieved by the following technical solutions:
A TiWAlN hard nanometer structural membrane, is that to take high-purity Ti target, W target, Al target be target, adopts two confocal radio frequency reactive sputterings of target to be deposited on Wimet or ceramic matrix, and divided thin film minor is expressed as Ti (W, Al, N), and thickness is at 1-3 μ m.
Ti target sputtering power 230-280W, W target sputtering power is 80-100W, Al target sputtering power is 0-100W; As Ti target power output 250W, W target power output is 90W, and when Al target power output is 75W, film has the friction and wear behavior of high rigidity (35.7GPa), the best.
A preparation method for TiWAlN hard nanometer structural membrane, is characterized in that, take high-purity Ti target, W target, Al target is target, utilizes two confocal radio frequency reactive sputterings of target to deposit and obtain on Wimet or ceramic matrix; During deposition, vacuum tightness is better than 3.0 * 10
-5pa, with the argon gas starting the arc, nitrogen is that reactant gases deposits, sputtering pressure 0.3Pa, argon nitrogen throughput ratio 10:(1-3); Ti target sputtering power 230-280W, W target sputtering power 80-100W, Al target sputtering power is 0-100W; Preferably, Ti target sputtering power 250W, W target sputtering power 90W, Al target sputtering power 0-100W; Preferably, Ti target sputtering power 250W, W target sputtering power 90W, Al target sputtering power is 25-100W; More preferably, Ti target sputtering power 250W, W target sputtering power 90W, Al target sputtering power 50-100W; Best, Ti target sputtering power 250W, W target sputtering power 90W, Al target sputtering power 75W, now, film hardness is up to 35.7GPa, and under dry cutting experiment, wear rate is 1.79 * 10
-8mm
3/ Nmm.
The preparation method of aforesaid TiWAlN hard nanometer structural membrane, is characterized in that, deposits in advance pure Ti as transition layer on matrix.
TiWAlN hard nanometer structural membrane of the present invention is to adopt high-purity Ti target, W target and the confocal RF-reactively sputtered titanium of Al target, be deposited on and prepare on Wimet or ceramic matrix, film thickness is at 1-3 μ m, in sputter reaction process, Al target power output is between 0-100W, and when Al target power output is 75W, the hardness of film is up to 35.7GPa, under dry cutting experiment, wear rate is 1.79 * 10
-8mm
3/ Nmm, this hard coat has comprehensively possessed high rigidity, the good characteristics of high-wearing feature.
Accompanying drawing explanation:
Fig. 1 is Ti, W and Al atomic percentage conc in embodiment of the present invention gained TiWAlN composite membrane.Because laboratory apparatus is inaccurate to the detection of N atom content, therefore by Ti, W and the normalization method of Al atom content, atom total content is set as 100%.Along with Al target sputtering power raises, in film, Al atom content increases, and Ti and W atom content correspondingly reduce.When Al target sputtering power rises to 25W gradually from 0W, 50W, 75W and 100W, the Al atom content of correspondence difference 0at.%, 5.26at.%, 10.39at.%, 15.91at.% and 23.08at.% in film.
Fig. 2 is the XRD figure spectrum of embodiment of the present invention gained TiWAlN composite membrane.As seen from the figure, Al atom content is when 0-10.39at.% scope, and film is by the TiWAlN phase of centroid structure, the Ti2N phase of hexagonal structure and the W of face-centred cubic structure
2n phase composite.When Al atom content increases to 15.91at.%, the Ti of hexagonal structure
2n disappears mutually; When Al atom content is 23.08at.%, the Al atom being solidly soluted in film reaches capacity, and excessive Al atom reacts the AlN phase that generates hexagonal structure with nitrogen, and now film is by TiWAlN phase and the W of face-centred cubic structure
2the AlN phase composite of N phase and hexagonal structure.
Fig. 3 is embodiment of the present invention gained TiWAlN composite membrane hardness (GPa) and unrelieved stress (GPa) and Al atom content (at.%) relation.Along with Al content increases, film hardness significantly raises, and when Al content is 15.91at.% (Al target power output 75W), film hardness is up to 35.7GPa; When Al content is during higher than 15.91at.%, along with Al content improves, film hardness declines gradually.
Fig. 4 is average friction coefficient and wear rate (mm under the dry cutting experiment of embodiment of the present invention gained TiWAlN composite membrane room temperature
3/ Nmm) with the relation of Al atom content (at.%).As seen from the figure, along with Al content increases, the frictional coefficient of TiWAlN composite membrane increases gradually, and wearing and tearing take the lead in reducing rear increase, and when Al content is 15.91at.% (Al target power output 75W), the wear rate of film obtains minimum value, is 1.79 * 10
-8mm
3/ Nmm.
Fig. 5 is average friction coefficient and wear rate (mm under the dry cutting experiment of embodiment of the present invention gained TiWAlN composite membrane (Al content is 15.91at.%)
3/ Nmm) with temperature (℃) variation relation.By figure, known, along with temperature raises, the frictional coefficient first increases and then decreases of TiWAlN composite membrane, and wear rate increases always.When temperature rises to 400 ℃, it is maximum that frictional coefficient reaches, and is 0.683; When temperature reaches 500 ℃, frictional coefficient sharply reduces, and when temperature rises to 700 ℃, the frictional coefficient of film is down to minimum, and 0.389.
Fig. 6 is the XRD figure spectrum of embodiment of the present invention gained TiWAlN composite membrane (Al content is 15.91at.%) under differing temps.As seen from the figure, when temperature is 400 ℃, in collection of illustrative plates, do not have the diffraction peak of oxide compound to occur; When temperature rises to 500 ℃, in film, there is TiO
2, Al
2o
3and WO
3diffraction peak.When temperature continues to rise to 700 ℃, TiO
2, Al
2o
3and WO
3diffraction peak strengthen, show that film is further oxidized.
Fig. 7 is the TG curve of embodiment of the present invention gained TiWAlN composite membrane (Al content is 15.91at.%).By graph discovery, when temperature is during lower than 430 ℃ of left and right, along with temperature raises, the weight of film slowly increases, and shows that a small amount of O atom enters in film, now forms amorphous Al in film
2o
3phase; When temperature surpasses 430 ℃ of left and right, the weight of film sharply raises, and shows that obvious oxidation, now Al have occurred film
2o
3by amorphous transition, be crystalline structure, at this result and 500 ℃ and 700 ℃, occurred Al
2o
3crystal XRD diffraction peak (Fig. 6) consistent.
Embodiment
Preparation method of the present invention, specific as follows:
The preparation of TiWAlN composite membrane completes on JGP-450 high-vacuum multi-target magnetic control sputtering equipment.This magnetic control sputtering device has three sputtering targets, is arranged on respectively in three water cooled holder, and three stainless steel baffle plates are arranged on respectively before three targets, by computer, automatically control.Pure Ti target (99.99%), pure W target (99.9%) and Al target (99.99%) are arranged on respectively three independently on radio frequency negative electrode, and target diameter is 75mm.Mirror polish is made in the Wimet such as rapid steel or ceramic matrix surface and process, to being filled with purity in vacuum chamber, be 99.999% Ar, N
2mixed gas, generates TiWAlN hard nanometer structure composite film by adopting pure Ti target, pure W target and Al target to carry out the confocal RF-reactively sputtered titanium method deposition of two targets on the matrix at the Wimet such as rapid steel or pottery.Before depositing Ti WAlN film, by baffle plate, isolate substrate and ion district, first with Ar ion pair target, carry out sputter 10min, to remove the impurity of target material surface, avoid impurity to bring in film.On matrix, deposit the pure Ti of 100nm as transition layer, to strengthen film-substrate cohesion.Sputtering time is 2h, and film thickness is 1-3 μ m.
Wherein, selecting substrate is that single crystalline Si sheet (100) is studied the composition of film, phase structure and hardness; Selecting substrate is the research that stainless composite membrane carries out friction and wear behavior.Substrate respectively cleans 10min respectively in acetone and dehydrated alcohol ultrasonic wave, to remove greasy dirt and the dust of matrix surface, packs in the rotatable substrate frame of vacuum chamber after flash baking.Target is about 11cm to the distance of substrate.Vacuum chamber base vacuum is better than 3.0 * 10
-5after Pa, pass into purity and be 99.999% the argon gas starting the arc.Operating air pressure remains on 0.3Pa, simultaneously Ar, N
2throughput ratio keeps 10:2.Fixedly Ti target power output is 250W, and W target sputtering power is 90W, prepares the TiWAlN film of a series of different al target power outputs (0-100W).
Embodiment 1-5 shown in table 1 has investigated the hardness of the TiWAlN film of different al target acquisition, frictional coefficient and the wear rate under dry cutting experiment.
Table 1
Embodiment 6-10 shown in table 2 has investigated at frictional wear temperature, and frictional coefficient and the wear rate under experiment cut in dry type friction:
Table 2
| ? | Temperature/℃ | Frictional coefficient | Wear rate/mm 3/Nmm |
| Embodiment 6 | Room temperature/25 ℃ | 0.574 | 1.79×10 -8 |
| Embodiment 7 | 200℃ | 0.608 | 2.404×10 -8 |
| Embodiment 8 | 400℃ | 0.633 | 4.012×10 -8 |
| Embodiment 9 | 500℃ | 0.464 | 1.842×10 -7 |
| Embodiment 10 | 700℃ | 0.389 | 3.244×10 -7 |
Above embodiment has only enumerated Ti target power output and has been fixed as 250W, W target power output is 90W, Al target power output is the situation of 0-100W, wherein Al target power output is 0 only as a comparison with reference to example, in actually operating, can operand power be Ti target power output 230-280W, W target sputtering power 80-100W, Al target sputtering power is 0-100W, the sputtering pressure 0.3Pa of deposition process, argon nitrogen throughput ratio 10:(1-3).
Claims (7)
1. a TiWAlN ganoine thin film, it is characterized in that take that high-purity Ti target, W target, Al target are target, adopts two confocal radio frequency reactive sputterings of target to be deposited on Wimet or ceramic matrix, divided thin film minor is expressed as Ti (W, Al, N), thickness is at 1-3 μ m; As Ti target power output 250W, W target power output is 90W, and when Al target power output is 75W, film has the friction and wear behavior of high rigidity (35.7GPa), the best.
2. a preparation method for TiWAlN ganoine thin film, is characterized in that, take high-purity Ti target, W target, Al target is target, utilizes two confocal radio frequency reactive sputterings of target to deposit and obtain on Wimet or ceramic matrix; During deposition, vacuum tightness is better than 3.0 * 10
-5pa, with the argon gas starting the arc, nitrogen is that reactant gases deposits, sputtering pressure 0.3Pa, argon nitrogen throughput ratio 10:(1-3); Ti target sputtering power 230-280W, W target sputtering power 80-100W, Al target sputtering power is 0-100W.
3. the preparation method of TiWAlN ganoine thin film according to claim 2, is characterized in that Ti target sputtering power 250W, W target sputtering power 90W, Al target sputtering power 0-100W.
4. the preparation method of TiWAlN ganoine thin film according to claim 2, is characterized in that Ti target sputtering power 250W, W target sputtering power 90W, and Al target sputtering power is 25-100W.
5. the preparation method of TiWAlN ganoine thin film according to claim 2, is characterized in that Ti target sputtering power 250W, W target sputtering power 90W, Al target sputtering power 50-100W.
6. the preparation method of TiWAlN ganoine thin film according to claim 2, is characterized in that Ti target sputtering power 250W, W target sputtering power 90W, and Al target sputtering power 75W, now, film hardness is up to 35.7GPa, and under dry cutting experiment, wear rate is 1.79 * 10
-8mm
3/ Nmm.
7. the preparation method of TiWAlN ganoine thin film according to claim 2, is characterized in that, deposits in advance pure Ti as transition layer on matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410282805.XA CN104073770B (en) | 2014-06-23 | 2014-06-23 | TiWAlN ganoine thin film and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410282805.XA CN104073770B (en) | 2014-06-23 | 2014-06-23 | TiWAlN ganoine thin film and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104073770A true CN104073770A (en) | 2014-10-01 |
| CN104073770B CN104073770B (en) | 2016-10-19 |
Family
ID=51595365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410282805.XA Expired - Fee Related CN104073770B (en) | 2014-06-23 | 2014-06-23 | TiWAlN ganoine thin film and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104073770B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267025A (en) * | 2018-11-16 | 2019-01-25 | 江苏科技大学 | The method for preparing Ti-Al-Ru-N nano-hard film based on ceramic substrate surface |
| CN109280885A (en) * | 2018-11-16 | 2019-01-29 | 江苏科技大学 | The method for preparing V-B-Al-N nano-hard film based on hard alloy or ceramic matrix surface |
| CN113445005A (en) * | 2021-05-21 | 2021-09-28 | 南昌大学 | Preparation method of low-stress TiW film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605324A (en) * | 2012-03-30 | 2012-07-25 | 马鞍山多晶金属材料科技有限公司 | Multi-arc ion plating superlattice nanometer composite coating and preparation method of multi-arc ion plating superlattice nanometer composite coating |
| CN102703859A (en) * | 2012-06-15 | 2012-10-03 | 上海大学 | Preparation method for gradient transitional layer between amorphous carbon-based film and metallic matrix |
| CN102776481A (en) * | 2012-06-15 | 2012-11-14 | 上海大学 | Method for preparing gradient transition layer between hard film and substrate |
-
2014
- 2014-06-23 CN CN201410282805.XA patent/CN104073770B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605324A (en) * | 2012-03-30 | 2012-07-25 | 马鞍山多晶金属材料科技有限公司 | Multi-arc ion plating superlattice nanometer composite coating and preparation method of multi-arc ion plating superlattice nanometer composite coating |
| CN102703859A (en) * | 2012-06-15 | 2012-10-03 | 上海大学 | Preparation method for gradient transitional layer between amorphous carbon-based film and metallic matrix |
| CN102776481A (en) * | 2012-06-15 | 2012-11-14 | 上海大学 | Method for preparing gradient transition layer between hard film and substrate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267025A (en) * | 2018-11-16 | 2019-01-25 | 江苏科技大学 | The method for preparing Ti-Al-Ru-N nano-hard film based on ceramic substrate surface |
| CN109280885A (en) * | 2018-11-16 | 2019-01-29 | 江苏科技大学 | The method for preparing V-B-Al-N nano-hard film based on hard alloy or ceramic matrix surface |
| CN109267025B (en) * | 2018-11-16 | 2020-10-09 | 江苏科技大学 | Method for preparing Ti-Al-Ru-N nano hard film based on ceramic substrate surface |
| CN113445005A (en) * | 2021-05-21 | 2021-09-28 | 南昌大学 | Preparation method of low-stress TiW film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104073770B (en) | 2016-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107620033B (en) | Preparation method of high-purity strong dense MAX phase coating | |
| CN104928638A (en) | AlCrSiN-based multilayer nanometer composite cutter coating layer and preparation method thereof | |
| CN102650030A (en) | TiMoN hard nanostructure film and preparation method thereof | |
| CN109402564B (en) | AlCrSiN and AlCrSiON double-layer nano composite coating and preparation method thereof | |
| Wu et al. | Al–Mg–B thin films prepared by magnetron sputtering | |
| CN104060231A (en) | TaN-Ag hard thin film and preparation method | |
| CN104073770A (en) | Tiwaln hard thin film and preparation method thereof | |
| CN103255373A (en) | TaVN composite coating and preparation method thereof | |
| CN101597751B (en) | Zr-Al-Si-N hard composite coating and preparation method thereof | |
| CN104032269A (en) | NbN-Ag hard thin film and preparation method thereof | |
| CN104532190A (en) | Preparation method of Zr-Cu metal glass film | |
| Zhao et al. | Compared the oxidation behavior of TiN and TiN/W2N ceramic coatings during heat treatment | |
| CN103898456B (en) | NbVN hard nanometer film and preparation method | |
| CN104099576A (en) | Hard film and preparation method thereof | |
| Das et al. | Strain induced FCC to BCC structural change in sputtered molybdenum thin films | |
| CN109338312B (en) | Silver-containing chromium nitride-based hard nano-structure composite film and preparation method thereof | |
| CN103898457B (en) | TiWN hard nanometer structural membrane and preparation method | |
| CN104109831A (en) | TiWCN hard film and preparing method thereof | |
| CN110527951B (en) | Composite lubricating film, preparation method thereof and workpiece | |
| CN108193178B (en) | A kind of crystalline state WC hard alloy film and its buffer layer technique room temperature growth method | |
| CN109576662B (en) | PVD (physical vapor deposition) technology-based bulk cermet/metal/cermet bidirectional nano gradient material and preparation method thereof | |
| CN102994945B (en) | ZrVN nano composite membrane and preparation method thereof | |
| CN103952672A (en) | TaCN (tantalum carbon nitrogen) hard nanostructured film and preparation method | |
| CN104005002B (en) | WAlN hard nanometer structural membrane and preparation method | |
| CN103898455A (en) | WBN hard nanostructure thin film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161019 Termination date: 20200623 |